Alkyl-and/or alkylene oligoglycoside betaine ester quaternaries

ABSTRACT

A composition containing an alk(en)yl oligoglycoside betaine esterquat corresponding to formula I: 
 
R 1 O(G) n OCOCR 2 R 3 NR 4 R 5 R 6   (I) 
 
wherein R 1  is an alk(en)yl group having from about 4 to about 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and n is a number from 1 to about 10, R 2  is H or a CH 3  group, R 3  is H or a linear and/or branched alk(en)yl group having from 1 to about 6 carbon atoms, R 4 , R 5  and R 6 , independently of one another, represent a linear and/or branched alk(en)yl group having from 1 to about 24 carbon atoms or a linear and/or branched hydroxyalk(en)yl group having from 1 to about 24 carbon atoms.

FIELD OF THE INVENTION

This invention relates to alk(en)yl oligoglycoside betaine esterquats,to a process for their production and to their use as emulsifiers, hairconditioners and fabric softeners.

PRIOR ART

By virtue of their excellent ecotoxicological properties, cationicsurfactants, such as esterquats for example, are acquiring increasingsignificance both in regard to fabric softeners and for cosmeticapplications. In cosmetic preparations, they may be present both inemulsions and lotions for skin care and in surface-active preparations,such as for example shampoos, shower baths, rinses, conditioners and thelike, for hair care. There is still a need on the market for newcationic surfactants which can be obtained from natural raw materialsources and which are highly hydrophilic by comparison with compoundsmade up solely of alkyl chains (for example cetyl trimethyl ammoniumchloride). This relatively high hydrophilia should not be obtained bythe introduction of alkoxide groups in order inter alia to reduceenvironmental pollution to a relatively low level.

Accordingly, the problem addressed by the present invention was toprovide new cationic surfactants, which could be produced from a naturalraw material source, would be free from ethylene and/or propylene oxideand would therefore cause relatively little environmental pollution, anda process for their production.

DESCRIPTION OF THE INVENTION

The present invention relates to alk(en)yl oligoglycoside betaineesterquats corresponding to formula (I):R¹O(G)_(n)OCOCR²R³NR⁴R⁵R⁶  (I)in which R¹ is an alk(en)yl group containing 4 to 22 carbon atoms, G isa sugar unit containing 5 or 6 carbon atoms and n is a number of 1 to10, R² is H or a CH₃ group, R³ is H or a linear and/or branchedalk(en)yl group containing 1 to 6 carbon atoms, R⁴, R⁵ and R⁶independently of one another represent a linear and/or branchedalk(en)yl group containing 1 to 24 carbon atoms or a linear and/orbranched hydroxyalk(en)yl group containing 1 to 24 carbon atoms.

The present invention also relates to a process for the production ofalk(en)yl oligoglycoside betaine esterquats, in which alk(en)yloligoglycosides corresponding to formula (II):R¹O(G)_(n)  (II)in which R¹ is an alk(en)yl group containing 4 to 22 carbon atoms, G isa sugar unit containing 5 or 6 carbon atoms and n is a number of 1 to10, are reacted with an α-halocarboxylic acid corresponding to formula(III):XCR²R³COOH  (III)in which R² is H or a CH₃ group, R³ is H or a linear and/or branchedalk(en)yl group containing 1 to 6 carbon atoms and X is halogen, andthen with tertiary amines corresponding to formula (IV):NR⁴R⁵R⁶  (IV)in which R⁴, R⁵ and R⁶ independently of one another represent a linearand/or branched alk(en)yl group containing 1 to 24 carbon atoms or alinear and/or branched hydroxyalkyl and/or hydroxyalkenyl groupcontaining 1 to 24 carbon atoms.

It has surprisingly been found that alk(en)yl oligoglycoside betaineesterquats, as new cationic sugar surfactants, can be produced byreacting alk(en)yl oligoglycosides with α-halocarboxylic acid andtertiary amines. It is of particular advantage that these newsurfactants emanate from a natural raw material source, are free fromethylene and/or propylene oxide and hence pose relatively little threatto the environment. In addition, the new cationic surfactants should behighly hydrophilic. Also, these compounds are suitable as conditionersfor the hair (hair rinses) and for fabrics (fabric softeners).

Alk(en)yl Oligoglycoside Betaine Esterquats

The present invention relates to alk(en)yl oligoglycoside betaineesterquats [alk(en)yl=alkyl and/or alkenyl] corresponding to formula(I):R¹O(G)_(n)OCOCR²R³NR⁴R⁵R⁶  (I)in which R¹ is an alk(en)yl group containing 4 to 22 carbon atoms, G isa sugar unit containing 5 or 6 carbon atoms and n is a number of 1 to10, R² is H or a CH₃ group, R³ is H or a linear and/or branchedalk(en)yl group containing 1 to 6 carbon atoms, R⁴, R⁵ and R⁶independently of one another represent a linear and/or branchedalk(en)yl group containing 1 to 24 carbon atoms or a linear and/orbranched hydroxyalk(en)yl group containing 1 to 24 carbon atoms.

A preferred embodiment of the invention is characterized by the use ofalk(en)yl oligoglycoside betaine esterquats corresponding to formula(I), in which R¹ is an alk(en)yl group containing 4 to 22 carbon atoms,G is a sugar unit containing 5 or 6 carbon atoms and n is a number of 1to 10, R² and R³ are H or a CH₃ group, preferably H, R⁴ and R⁵independently of one another represent a linear and/or branchedalk(en)yl group containing 1 to 6 carbon atoms or a linear and/orbranched hydroxyalkyl and/or hydroxyalkenyl alkenyl group containing 1to 6 carbon atoms and preferably a CH₃ group or a hydroxyethyl group, R⁶is a linear and/or branched alk(en)yl group containing 1 to 24 carbonatoms or a linear and/or branched hydroxyalkyl and/or hydroxyalkenylgroup containing 1 to 24 carbon atoms.

Another embodiment of the invention is characterized by the use ofalk(en)yl oligoglycoside betaine esterquats corresponding to formula(I), in which R¹ is an alk(en)yl group containing 4 to 22 carbon atoms,G is a sugar unit containing 5 or 6 carbon atoms and n is a number of 1to 10, R² and R³ are H, R⁴ and R⁵ represent a CH₃ group or ahydroxyethyl group, R⁶ is a linear and/or branched alk(en)yl groupcontaining 1 to 24 carbon atoms or a linear and/or branched hydroxyalkyland/or hydroxyalkenyl group containing 1 to 24 carbon atoms.

The alk(en)yl oligoglycoside betaine esterquats according to theinvention are used in surface-active preparations, preferably in laundrydetergents, dishwashing detergents and cleaning products, and cosmeticand/or pharmaceutical preparations in quantities of 0.01 to 60% byweight, preferably in quantities of 0.05 to 30% by weight and moreparticularly in quantities of 2.5 to 20% by weight, based on the activesubstance content.

Production of Alk(en)yl Glycerol Ether Carboxylic Acids

The alk(en)yl oligoglycoside betaine esterquats are obtained by reactionof alk(en)yl oligoglycosides corresponding to formula (II) withα-halocarboxylic acids corresponding to formula (III) and tertiaryamines corresponding to formula (IV). The preferred alk(en)yloligoglycoside betaine esterquats obtainable by this reaction werementioned in the previous chapter.

Alkyl and alkenyl oligoglycosides are known nonionic surfactants whichcorrespond to formula (II):R¹O-[G]_(n)  (II)where R¹ is an alk(en)yl group containing 4 to 22 carbon atoms, G is asugar unit containing 5 or 6 carbon atoms and n is a number of 1 to 10.They may be obtained by the relevant methods of preparative organicchemistry. The overviews presented by Bierman et al. in Starch/Stärke45, 281 (1993), by B. Salka in Cosm. Toil. 108, 89 (1993) and by J.Kahre in SÖFW-Journal No. 8, 598 (1995) are cited as representative ofthe extensive literature available on this subject.

The alk(en)yl oligoglycosides may be derived from aldoses or ketosescontaining 5 or 6 carbon atoms, preferably glucose. Accordingly, thepreferred alk(en)yl oligoglycosides are alk(en)yl oligoglucosides. Theindex n in general formula (II) indicates the degree of oligomerization(DP), i.e. the distribution of mono- and oligoglycosides, and is anumber of 1 to 10. Whereas n in a given compound must always be aninteger and, above all, may assume a value of 1 to 6, the value n for acertain alkyl oligoglycoside is an analytically determined calculatedquantity which is generally a broken number. Alk(en)yl oligoglycosideshaving an average degree of oligomerization n of 1.1 to 3.0 arepreferably used. Alk(en)yl oligoglycosides having a degree ofoligomerization of less than 1.7 and, more particularly, between 1.2 and1.4 are preferred from the applicational perspective. The alkyl oralkenyl radical R¹ may preferably be derived from primary alcoholscontaining 4 to 11 and preferably 8 to 10 carbon atoms. Typical examplesare butanol, caproic alcohol, caprylic alcohol, capric alcohol andundecyl alcohol and the technical mixtures thereof obtained, forexample, in the hydrogenation of technical fatty acid methyl esters orin the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyloligoglucosides having a chain length of C₈ to C₁₀ (DP=1 to 3), whichare obtained as first runnings in the separation of technical C₈₋₁₈coconut oil fatty alcohol by distillation and which may contain lessthan 6% by weight of C₁₂ alcohol as an impurity, and also alkyloligoglucosides based on technical C_(9/11) oxoalcohols (DP=1 to 3) arepreferred. In addition, the alkyl or alkenyl radical R¹ may preferablybe derived from primary alcohols containing 12 to 22 and preferably 12to 14 carbon atoms. Typical examples are lauryl alcohol, myristylalcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearylalcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachylalcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidylalcohol and technical mixtures thereof which may be obtained asdescribed above. Alkyl oligoglucosides based on hydrogenated C_(12/14)coconut oil fatty alcohol having a DP of 1 to 3 are preferred.

α-Halocarboxylic acids may be obtained by the relevant methods oforganic chemistry and correspond to formula (III):XCR²R³COOH  (III)in which R² is H or a CH₃ group, R³ is H or a linear and/or branchedalk(en)yl group containing 1 to 6 carbon atoms and X is halogen. In oneparticular embodiment of the invention, R² and R³ represent H or a CH₃group, more particularly H. More particularly, α-haloacetic acid, forexample monochloroacetic acid, is used.

Tertiary amines which may be used for the purposes of the inventioncorrespond to formula (IV):NR⁴R⁵R⁶  (IV)in which R⁴, R⁵ and R⁶ independently of one another represent a linearand/or branched alk(en)yl group containing 1 to 24 carbon atoms or alinear and/or branched hydroxyalkyl and/or hydroxyalkenyl groupcontaining 1 to 24 carbon atoms. In one particular embodiment of theinvention, R⁴ and R⁵ independently of one another represent a linearand/or branched alk(en)yl group containing 1 to 6 carbon atoms or alinear and/or branched hydroxyalkyl and/or hydroxyalkenyl groupcontaining 1 to 6 carbon atoms and R⁶ is a linear and/or branchedalk(en)yl group containing 1 to 24 carbon atoms or a linear and/orbranched hydroxyalkyl and/or hydroxyalkenyl group containing 1 to 24carbon atoms. In another embodiment of the invention, R⁴ and R⁵independently of one another represent a CH₃ group or a hydroxyethylgroup and R⁶ is a linear and/or branched alk(en)yl group containing 1 to24 carbon atoms or a linear and/or branched hydroxyalkyl and/orhydroxyalkenyl group containing 1 to 24 carbon atoms, preferably alinear and/or branched alk(en)yl group containing 1 to 24 carbon atomsor a linear and/or branched hydroxyalkyl and/or hydroxyalkenyl groupcontaining 1 to 6 carbon atoms.

Accordingly, the tertiary amine may be derived from short-chain tertiaryamines, preferably dimethyl ethanolamine, triethanolamine and methyldiethanolamine, or long-chain amines, preferably dimethyl cocoamine,dimethyl laurylamine and dimethyl tallow amine.

To produce the compounds according to the invention, the alk(en)yloligoglycoside is dried beforehand to a water content of at most 5% byweight and preferably at most 4% by weight, based on the activesubstance content of the alk(en)yl oligoglycoside, and then introducedinto a reaction vessel for the reaction. The alk(en)yl oligoglycoside isthen esterified with the α-halocarboxylic acid in a molar ratio of 1:0.5to 1:3 and preferably 1:1 to 1:1.5, the reaction being carried out withremoval of water over a period of 5 to 13 hours and preferably 7 to 12hours at a temperature of 100 to 130° C. and preferably 115 to 120° C.and in the presence of up to 50% of an organic solvent, based on thereaction mixture as a whole. The organic solvent used is preferablytoluene, benzene or xylene, more particularly toluene. The reactionproduct obtained is then reacted with a tertiary amine corresponding toformula (IV) in a molar ratio of 1:0.5 to 1:3 and preferably 1:1 to1:1.5 at a temperature of 70 to 100° C. and preferably 80 to 90° C.Organic solvent is added to the tertiary amine beforehand in such aquantity that the reaction mixture is readily stirrable. The reaction isterminated when the theoretical quantity of inorganic halide released isreached. The reaction times are normally 30 minutes to 3 hours andpreferably 50 minutes to 1.5 hours.

COMMERCIAL APPLICATIONS

The alk(en)yl oligoglycoside betaine esterquats according to theinvention may be adjusted to any concentration by addition of water; thewater content is preferably 20 to 85% by weight, more preferably 20 to75% by weight and most preferably 50 to 70% by weight.

The alk(en)yl oligoglycoside betaine esterquats may be used assurfactants in surface-active preparations. Surface-active preparationsin the context of the invention are preferably understood to be laundrydetergents, dishwashing detergents and cleaning products and alsocosmetic and/or pharmaceutical preparations, more particularly cosmeticand/or pharmaceutical preparations. More particularly, the productsaccording to the invention may be used in hair conditioners and fabricsofteners. These surface-active preparations may contain pearlizingwaxes, consistency factors, thickeners, superfatting agents,stabilizers, silicone compounds, fats, waxes, antioxidants, antidandruffagents, swelling agents, tyrosine inhibitors, hydrotropes, solubilizers,preservatives, perfume oils, dyes, other surfactants and otheringredients typical, for example, of laundry detergents, dishwashingdetergents and cleaning products as further auxiliaries and additives.Preferred cosmetic and/or pharmaceutical preparations are oral hygieneand dental care preparations, hair shampoos, hair lotions, foam baths,shower baths, creams, lotions, gels, emulsions, wax/fat compounds, stickpreparations or ointments. Besides the alk(en)yl oligoglycoside betaineesterquats according to the invention, these surface-active preparationsmay contain other known ingredients typical of the particularapplication in the usual concentrations.

The preparations according to the invention show not only conditioningproperties [conditioners] for hair (hair rinses) and fabrics (fabricsofteners), but also foaming and cleaning properties. In addition,relatively long-chain alk(en)yl oligoglycoside betaine esterquats, suchas C_(16/18) oligoglycoside betaine esterquats for example, can haveemulsifying properties and may therefore be used in cosmetic and/orpharmaceutical preparations. Accordingly, the present invention alsorelates to the use of the alk(en)yl oligoglycoside betaine esterquats ashair conditioners, as fabric softeners and as emulsifiers. Moreparticularly, C_(16/18) alkyl oligoglycoside betaine esterquats may beused as emulsifiers in all types of emulsions known to the expert.

Typical cosmetic and/or pharmaceutical cleaning preparations preferablyhave the following composition, based on the active substance content:

-   (a) 0.05 to 20, preferably 0.5 to 10 and more particularly 2.5 to    18% by weight alk(en)yl oligoglycoside betaine esterquats,-   (b) 0.05 to 15, preferably 0.5 to 10 and more particularly 2.5 to    7.5% by weight betaines and optionally-   (c) 0 to 15, preferably 0.5 to 10 and more particularly 2.5 to 7.5%    by weight anionic surfactants,    with the proviso that the quantities shown add up to 100% by weight    with water and optionally other auxiliaries and additives.

Typical liquid laundry/dishwashing detergents and cleaners preferablyhave the following composition, based on the active substance content:

-   (a) 2.5 to 30, preferably 7 to 25 and more particularly 10 to 20% by    weight alk(en)yl oligoglycoside betaine esterquats,-   (b) 0.05 to 15, preferably 0.5 to 10 and more particularly 2.5 to    7.5% by weight betaines and optionally-   (c) 2.5 to 30, preferably 7 to 25 and more particularly 10 to 20% by    weight anionic surfactants,    with the proviso that the quantities shown add up to 100% by weight    with water and optionally other auxiliaries and additives.

Typical cosmetic and/or pharmaceutical emulsions preferably have thefollowing composition, based on the active substance content:

-   (a) 0.05 to 15, preferably 0.5 to 10 and more particularly 1 to 5%    by weight alk(en)yl oligoglycoside betaine esterquats, preferably    C_(16/18) alkyl oligoglycoside betaine esterquats,-   (b) 3 to 30, preferably 5 to 20 and more particularly 7 to 15% by    weight oil components and optionally-   (c) 0.5 to 20 and preferably 2.5 to 10% by weight consistency    factors,    with the proviso that the quantities shown add up to 100% by weight    with water and optionally other auxiliaries and additives.

EXAMPLES

The following Examples are intended to illustrate the invention withoutlimiting it in any way.

Example 1 (a) Preparation of C_(12/14) Alkyl Oligoglycoside ChloroaceticAcid Ester

In a 1-liter three-necked flask, 61.4 g (0.65 mol) chloroacetic acidwere added to 214.0 g (0.5 mol) of a citric-acid-neutralized,freeze-dried C_(12/14) alkyl oligoglycoside (water-free, 1.7% by weightwater; based on Plantacare 1200 UP, Cognis) with elimination of water ata temperature of 115-120° C. and in the presence of 250 ml addedtoluene. The reaction was terminated after 11.25 h. 513.4 g of a darkyellow, cloudy and liquid product were obtained. The alkyloligoglucoside conversion amounted to 70.6%. acid value: 19.9saponification value: 158.0 free monoglucosides (GC) 8.1% freediglucosides (GC) 4.6% free triglucosides (GC) 0.8% free tetraglucosides(GC) 0.3% free pentaglucosides (GC) 0.1%

(b) Preparation of Cationic C_(12/14) Alkyl Oligoglycoside BetaineEsterquat

In a 500 ml three-necked flask, 29.0 g (0.3 mol) of the C_(12/14) alkyloligoglycoside chloroacetic acid ester prepared in (a) were reacted with27.6 g (0.3 mol) N,N-dimethyl ethanolamine at 80° C. in 220 g toluene.The reaction was terminated after 1.25 h when the theoretical quantityof inorganic chloride (2.82%) had been released. The solvent—toluene—wasdistilled off in vacuo (35 mbar) at 60 to 80° C. in a rotary evaporator.The product was adjusted with water to a concentration of 30% activesubstance. The product was a dark brown liquid.

(c) Preparation of a Cationic C_(12/14) Alkyl Oligoglucoside BetaineEsterquat Based on N,N-Dimethyl Octyl/Decyl Amine

In a 250 ml three-necked flask, 41.5 g (96.7 mmol) of the C_(12/14) APGchloroacetic acid ester prepared in a) were reacted with 17.2 g (96.7mmol) N,N-dimethyl octyl/decyl amine at 80° C. in 36.7 g toluene. Thereaction was terminated after 1 hour 10 minutes when the theoreticalquantity of inorganic chloride (4.05%) had been released. After additionof 250 g water, the toluene was distilled off in a water separator forheavy solvents. The pH was then adjusted to 6.4 A yellow, homogeneousliquid product was obtained. cationic surfactant content: 17.4% dryresidue: 24.0%

1-9. (cancelled).
 10. A composition comprising an alk(en)yloligoglycoside betaine esterquat corresponding to formula I:R¹O(G)_(n)OCOCR²R³NR⁴R⁵R⁶  (I) wherein R¹ is an alk(en)yl group havingfrom about 4 to about 22 carbon atoms, G is a sugar unit containing 5 or6 carbon atoms and n is a number from 1 to about 10, R² is H or a CH₃group, R³ is H or a linear and/or branched alk(en)yl group having from 1to about 6 carbon atoms, R⁴, R⁵ and R⁶, independently of one another,represent a linear and/or branched alk(en)yl group having from 1 toabout 24 carbon atoms or a linear and/or branched hydroxyalk(en)yl grouphaving from 1 to about 24 carbon atoms.
 11. The composition of claim 10wherein the alk(en)yl oligoglycoside betaine is present in thecomposition in an amount of from about 0.01 to 60% by weight, based onthe weight of the composition.
 12. The composition of claim 10 whereinthe alk(en)yl oligoglycoside betaine is present in the composition in anamount of from about 0.05 to 30% by weight, based on the weight of thecomposition.
 13. The composition of claim 10 wherein the alk(en)yloligoglycoside betaine is present in the composition in an amount offrom about 2.5 to 20% by weight, based on the weight of the composition.14. The composition of claim 10 wherein in formula I, R² and R³ are H,R⁴ and R⁵ represent a methyl group or a hydroxyethyl group.
 15. Thecomposition of claim 10 further comprising a co-surfactant selected fromthe group consisting of a betaine, an anionic surfactant, and mixturesthereof.
 16. A process for making an alk(en)yl oligoglycoside betaineesterquat comprising: (a) providing an alk(en)yl oligoglycosidecorresponding to formula (II):R¹O(G)_(n)  (II)  wherein R¹ is an alk(en)yl group having from about 4to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms andn is a number of 1 to 10; (b) providing an α-halocarboxylic acidcorresponding to formula (III):XCR²R³COOH  (III)  wherein R² is H or a CH₃ group, R³ is H or a linearand/or branched alk(en)yl group having from 1 to about 6 carbon atomsand X is a halogen; (c) reacting (a) and (b) to form a reaction product;(d) providing a tertiary amines corresponding to formula (IV):NR⁴R⁵R⁶  (IV)  wherein R⁴, R⁵ and R⁶, independently of one another,represent a linear and/or branched alk(en)yl group having from 1 toabout 24 carbon atoms or a linear and/or branched hydroxyalkyl and/orhydroxyalkenyl group having from 1 to about 24 carbon atoms; and (e)reacting the reaction product of (c) with (d) to form the alk(en)yloligoglycoside betaine.
 17. The process of claim 16 wherein thealk(en)yl oligoglycoside of (a) has a water content of up to 5% byweight.
 18. The process of claim 16 wherein the alk(en)yl oligoglycosideof (a) and the α-halocarboxylic acid of (b) are reacted in a molar ratioof from about 1:0.5 to 1:3.
 19. The process of claim 16 wherein thealk(en)yl oligoglycoside of (a) and the α-halocarboxylic acid of (b) arereacted in a molar ratio of from about 1:1 to 1:1.5.
 20. The process ofclaim 16 wherein the reaction product of (c) and the tertiary amine of(d) are reacted in a molar ratio of from about 1:0.5 to 1:3.
 21. Theprocess of claim 16 wherein the reaction product of (c) and the tertiaryamine of (d) are reacted in a molar ratio of from about 1:0.5 to 1:3.